WO2021143713A1 - Procédé de préparation d'intermédiaire de l-glufosinate-ammonium - Google Patents
Procédé de préparation d'intermédiaire de l-glufosinate-ammonium Download PDFInfo
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- WO2021143713A1 WO2021143713A1 PCT/CN2021/071426 CN2021071426W WO2021143713A1 WO 2021143713 A1 WO2021143713 A1 WO 2021143713A1 CN 2021071426 W CN2021071426 W CN 2021071426W WO 2021143713 A1 WO2021143713 A1 WO 2021143713A1
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- Prior art keywords
- group
- alkyl
- formula
- compound
- alkyl group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 aliphatic amines Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000006239 protecting group Chemical group 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000005002 naphthylamines Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 8
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 102000011759 adducin Human genes 0.000 description 7
- 108010076723 adducin Proteins 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- PMVVRSKJCGEFIY-UHFFFAOYSA-N methylphosphonous acid Chemical compound CP(O)O PMVVRSKJCGEFIY-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VWBDUAZQYFRETJ-JEDNCBNOSA-N ethyl (2S)-2-(chloroamino)-4-hydroxybutanoate hydrochloride Chemical compound CCOC(=O)[C@H](CCO)NCl.Cl VWBDUAZQYFRETJ-JEDNCBNOSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XBKCXPRYTLOQKS-DFWYDOINSA-N [(3s)-2-oxooxolan-3-yl]azanium;chloride Chemical compound Cl.N[C@H]1CCOC1=O XBKCXPRYTLOQKS-DFWYDOINSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- AWONIZVBKXHWJP-UHFFFAOYSA-N 1-methoxy-2,3,5-trimethylbenzene Chemical compound COC1=CC(C)=CC(C)=C1C AWONIZVBKXHWJP-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 0 CP(*)(CC[C@@](C(*)=O)N*)=O Chemical compound CP(*)(CC[C@@](C(*)=O)N*)=O 0.000 description 1
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N CP(CC[C@@H](C(O)=O)N)(O)=O Chemical compound CP(CC[C@@H](C(O)=O)N)(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QJPWUUJVYOJNMH-VKHMYHEASA-N L-homoserine lactone Chemical compound N[C@H]1CCOC1=O QJPWUUJVYOJNMH-VKHMYHEASA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- AEDAWHHRIHMZAR-UHFFFAOYSA-N [O-][N+](=O)CN1CCCC1=O Chemical compound [O-][N+](=O)CN1CCCC1=O AEDAWHHRIHMZAR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- CFXLTWWKEOMXOK-YFKPBYRVSA-N ethyl (2S)-2-(chloroamino)-4-hydroxybutanoate Chemical compound CCOC(=O)[C@H](CCO)NCl CFXLTWWKEOMXOK-YFKPBYRVSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- UWWYIHQMACYNDL-UHFFFAOYSA-N methylphosphinous acid Chemical compound CPO UWWYIHQMACYNDL-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the present invention relates to a method for preparing L-glufosinate-ammonium intermediate.
- Glufosinate-ammonium is an important herbicide.
- the present invention provides a method for preparing enantiomerically pure compounds of formula (I) and salts thereof,
- the method includes the following steps:
- Hal is halogen
- PG is hydrogen or an amino protecting group
- Z is OX or OY
- R 1 is a C 1 -C 16 alkyl, cyclohexyl, cyclopentyl or phenyl group, wherein each group can be hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or dioxane Amino substitution;
- R 2 is a C 1 -C 8 alkyl group, a C 1 -C 8 ether group or a phenyl group;
- X and Y are each independently an alkyl group, an alkenyl group or an aryl group
- R 2 is a C 1 -C 6 alkyl group, preferably a C 1 -C 4 alkyl group.
- the aforementioned base is an organic base or an inorganic base, preferably an organic base.
- the aforementioned organic base is selected from organic amines, pyridines or pyridine derivatives having 1 to 3 substituents attached to one or more carbon atoms of the heterocyclic ring, piperidines or having 1 to 3 attached to the A piperidine derivative with a substituent on one or more carbon atoms of a heterocyclic ring.
- the aforementioned organic amine is selected from aliphatic amines, alcohol amines, amides, alicyclic amines, aromatic amines or naphthylamines, preferably aliphatic amines; the aforementioned substituents are each independently selected from lower alkyl groups, lower alkoxy groups, and hydroxy lower alkyl groups. Group, amino group, lower alkylamino group and lower alkylamino lower alkyl group, lower alkyl group and lower alkoxy group are preferred.
- the aforementioned inorganic base is selected from alkali metal hydroxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates or alkaline earth metal hydrogen carbonates.
- R 1 is a phenyl group or a C 1 -C 6 alkyl group, preferably a C 1 -C 4 alkyl group, more preferably a methyl group.
- X and Y are each independently a C 1 -C 6 alkyl group, preferably a C 1 -C 4 alkyl group.
- R 1 is methyl
- X is ethyl
- Y is ethyl
- the aforementioned enantiomer ratio is (L):(D)-enantiomer or (D):(L)-enantiomer from 50.5:49.5 to 99.5:0.5.
- the aforementioned enantiomer ratio is (L):(D)-enantiomers ranging from 50.5:49.5 to 99.5:0.5.
- the reaction can occur at room temperature, and the temperature of the reaction may be 20 to 200°C. Taking the efficiency of the reaction into consideration, it is preferably 90 to 140°C. If the temperature is too low, the reaction rate is too slow, and if the temperature is too high, by-products will be formed.
- the aforementioned reaction can be carried out in a solvent-free condition or in an inert solvent. Adding solvent can reduce the generation of impurities and increase the reaction time.
- the inert solvent may be selected from any one or more of benzene solvents, amide solvents, halogenated hydrocarbon solvents, ether solvents or ester solvents.
- the inert solvent can be selected from chlorobenzene, trimethylbenzene, 1,4-dioxane, 1,2-dichloroethane, dimethyl sulfoxide, nitromethylpyrrolidone, N,N-dimethyl Any one or more of methyl formamide, petroleum ether, n-heptane, tetrahydrofuran, methyltetrahydrofuran, benzene, toluene, ethyl acetate, and butyl acetate.
- the solvent has a certain influence on the reaction effect, preferably benzene, trimethylbenzene, 1,4-dioxane, 1,2-dichloroethane, dimethyl sulfoxide, nitrogen methyl pyrrolidone, N, N-dimethyl methyl Amide.
- the foregoing reaction can adopt a variety of feeding methods.
- the compound of formula (II) and the compound of formula (III) can be mixed first, and the base is added to it; the compound of formula (II) and the base are first mixed, and the compound of formula (III) is added to it.
- the molar ratio of the aforementioned base to the compound of formula (II) is 1:(1-100), preferably 1:(2-10).
- the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:(1-10), preferably 1:(1.3-2).
- the reaction time can be varied within a wide range, depending on the temperature, operating conditions and batch size, it can be 0.5 to 48 hours.
- the present invention also provides a method for preparing L- glufosinate-ammonium, which includes the following steps:
- PG, Z and R 2 are as defined above.
- the present invention also provides a compound of formula (I) or a salt, enantiomer or a mixture of enantiomers in all ratios,
- PG, Z, R 1 and R 2 are as defined above;
- the method of the present invention can effectively maintain the ee value of the raw materials by adding alkali, and the organic alkali has the better effect.
- amino protecting group refers to a group that can be attached to a nitrogen atom on an amino group so as to protect the amino group from participating in the reaction and which can be easily removed in a subsequent reaction.
- Suitable amino protecting groups include, but are not limited to the following protecting groups:
- alkyl refers to saturated aliphatic hydrocarbon groups, including straight and branched chain groups of 1 to 18 carbon atoms. Preferred are alkyl groups containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl and the like.
- the alkyl group may be substituted or unsubstituted. When substituted, the substituent may be halogen, nitro, sulfonyl, etheroxy, etherthio, ester, thioester, or cyano.
- alkenyl refers to an alkyl group as defined above composed of at least two carbon atoms and at least one carbon-carbon double bond. For example, vinyl, 1-propenyl, 2-propenyl, 1-, 2- or 3-butenyl and the like.
- the alkenyl group may be substituted or unsubstituted. When substituted, the substituent may be a halogen, a nitro group, a sulfonyl group, an etheroxy group, an etherthio group, an ester group, a thioester group, or a cyano group.
- aromatic group refers to a group having at least one aromatic ring structure.
- the aromatic group is preferably phenyl or benzyl.
- the phenyl and benzyl groups may be substituted or unsubstituted.
- the C 1 -C 4 alkyl group is straight or branched and contains a saturated hydrocarbon chain of 1 to 4 carbon atoms. It can be a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl group.
- the temperature of the system was maintained at 10°C, and the reaction was stirred for 30 minutes. The temperature was gradually increased to 35°C, and the reaction was stirred for 20 hours. During the process, bubbles continued to be generated. The progress of the reaction was monitored by LC-MS and the reaction was terminated. Among them, the intermediate product (chlorohomoserine ethyl ester hydrochloride), ester impurities, and ether impurities are all LC detection values. The temperature of the system was lowered to room temperature, and the remaining thionyl chloride and ethanol were removed by distillation under reduced pressure.
- the chlorohomoserine ethyl ester hydrochloride solid was reacted with saturated sodium carbonate solution, the pH of the system was adjusted to 7-8, and ethyl acetate was added for extraction, and the total extraction was 3 times.
- the amount of ethyl acetate for the 3 extraction processes was 30 mL. , 10mL and 10mL.
- the organic phase was collected and concentrated to obtain 10.30g of the target oily compound chlorohomoserine ethyl ester (165.62g/mol, 0.0591mol), HPLC purity 95%, ee value 99%, based on the intermediate product chlorohomoserine ethyl ester hydrochloric acid
- the salt yield is 90%.
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- Organic Chemistry (AREA)
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Abstract
La présente invention concerne un procédé de préparation d'un intermédiaire de L-glufosinate-ammonium.
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| CN202180006003.4A CN114585631A (zh) | 2020-01-13 | 2021-01-13 | 制备l-草铵膦中间体的方法 |
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| CN202010030973.5 | 2020-01-13 | ||
| CN202010030973 | 2020-01-13 |
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| WO2021143713A1 true WO2021143713A1 (fr) | 2021-07-22 |
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| PCT/CN2021/071426 WO2021143713A1 (fr) | 2020-01-13 | 2021-01-13 | Procédé de préparation d'intermédiaire de l-glufosinate-ammonium |
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| WO (1) | WO2021143713A1 (fr) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021147894A1 (fr) * | 2020-01-20 | 2021-07-29 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate-ammonium |
| CN115583967A (zh) * | 2022-09-22 | 2023-01-10 | 佳木斯黑龙农药有限公司 | 一种精草铵膦的制备方法 |
| CN115636849A (zh) * | 2022-09-09 | 2023-01-24 | 河北威远生物化工有限公司 | 一种l-草铵膦的合成方法 |
| WO2023109757A1 (fr) * | 2021-12-13 | 2023-06-22 | 利尔化学股份有限公司 | Dérivé de l-glufosinate, composition le comprenant, son procédé de préparation et son utilisation |
| CN116284115A (zh) * | 2023-03-22 | 2023-06-23 | 佳木斯黑龙农药有限公司 | 一种精草铵膦中间体的制备方法 |
| CN116284116A (zh) * | 2023-03-22 | 2023-06-23 | 佳木斯黑龙农药有限公司 | 一种精草铵膦中间体的制备方法 |
| TWI823808B (zh) * | 2022-11-17 | 2023-11-21 | 大陸商永農生物科學有限公司 | 草銨膦的製備方法 |
| WO2024114790A1 (fr) * | 2022-12-02 | 2024-06-06 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate-ammonium ou d'un dérivé de celui-ci |
| WO2024146621A1 (fr) * | 2023-01-06 | 2024-07-11 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate ou d'un dérivé de celui-ci |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117820363A (zh) * | 2022-09-27 | 2024-04-05 | 摩珈(上海)生物科技有限公司 | 利用膦试剂制备l-草铵膦的方法 |
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| CN102584893B (zh) * | 2012-02-07 | 2015-03-04 | 浙江工业大学 | 一种草铵膦的制备方法 |
| CN103374030B (zh) * | 2012-04-13 | 2016-03-23 | 浙江新安化工集团股份有限公司 | 一种制备草铵膦的方法及其中间体的制备方法 |
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2021
- 2021-01-13 CN CN202180006003.4A patent/CN114585631A/zh active Pending
- 2021-01-13 WO PCT/CN2021/071426 patent/WO2021143713A1/fr active Application Filing
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021147894A1 (fr) * | 2020-01-20 | 2021-07-29 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate-ammonium |
| US11680077B2 (en) | 2020-01-20 | 2023-06-20 | Lier Chemical Co., Ltd. | Preparation method for glufosinate |
| WO2023109757A1 (fr) * | 2021-12-13 | 2023-06-22 | 利尔化学股份有限公司 | Dérivé de l-glufosinate, composition le comprenant, son procédé de préparation et son utilisation |
| CN115636849A (zh) * | 2022-09-09 | 2023-01-24 | 河北威远生物化工有限公司 | 一种l-草铵膦的合成方法 |
| CN115583967A (zh) * | 2022-09-22 | 2023-01-10 | 佳木斯黑龙农药有限公司 | 一种精草铵膦的制备方法 |
| TWI823808B (zh) * | 2022-11-17 | 2023-11-21 | 大陸商永農生物科學有限公司 | 草銨膦的製備方法 |
| WO2024114790A1 (fr) * | 2022-12-02 | 2024-06-06 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate-ammonium ou d'un dérivé de celui-ci |
| WO2024146621A1 (fr) * | 2023-01-06 | 2024-07-11 | 利尔化学股份有限公司 | Procédé de préparation de glufosinate ou d'un dérivé de celui-ci |
| CN116284115A (zh) * | 2023-03-22 | 2023-06-23 | 佳木斯黑龙农药有限公司 | 一种精草铵膦中间体的制备方法 |
| CN116284116A (zh) * | 2023-03-22 | 2023-06-23 | 佳木斯黑龙农药有限公司 | 一种精草铵膦中间体的制备方法 |
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